Monoazo thiazole dyestuffs



United States Patent 3,169,954 MONOAZO THIAZOLE DYESTUFFS .Iames M. Straley and John G. Fisher, Kingsport, Tenn, assignors to Eastman Kodak Company, Rochester, N .Y., a corporation of New Jersey N0 Drawing. Filed Aug. 6, 1962, Ser. No. 214,832 8 Claims. (Cl. 260-158) This invention relates to monoazo dyestuffs particularly useful for dyeing acrylic fibers.

The dyes are obtained by coupling diazo salts of certain Z-aminothiazoles with various amine coupling compomats and have the following general formula wherein R'=an aniline coupling component free of carboxyl or sulfo groups or hydroxyl groups ortho to the azo linkage e.g. lower dialkyl aniline, N-ethyl-N-B-hydroxyethylaniline, di-B-hydroxyethylaniline, N-fi-hydroxyethyldiphenylamine,N,N,-diethyl-m-chloroaniline, N-fi cyanoethyldiphenylamine, N-cyanoethylaniline, etc.,

R and R are different and represent (not simultaneously) hydrogen, lower alkyl, lower dialkylaminomethyl, morpholinomethyl, piperidinomethyl, or other reduced heterocyclic radical, illustrated hereinafter. A preferred group of dyes particularly etlicacious for dyeing acrylic fibers have the above general formula wherein R is as above, R is a morpholinomethyl or piperidinomethyl radical and R is hydrogen or lower alkyl such as methyl, ethyl, propyl or butyl.

The dyes are therefore characterized by containing in either the 4- or 5-positions of the thiazole nucleus, a morpholinomethyl, piperidinomethyl or lower dialkylaminomethyl radical and the nuclear position not containing one of these groups may be unsubstituted or substituted with, for example, lower alkyl or aryl radical of the benzene series including phenyl and substituted phenyl. In the mentioned preferred group of compounds one of the 4- or 5-positions is substituted with morpholinomethyl or piperidinomethyl radicals and the other position is unsubstituted or contains an alkyl radical. The dyes are distinctive for use in dyeing acrylic fibers compared to known azo dyes obtained from other Z-aminothiazoles substituted in the 4- and 5-positions. v

The Z-aminothiazoles compounds used in invention are prepared by hydrolysis ofthe corresponding acetylated derivatives prepared as described in Sprague, Land, Ziegler, J. A. C. S., 68, 2155 (1946), and Albertson, 70, 669-670 (1948), as illustrated in the following examples.

2-AMINO-5-MORPHOLINOMETHYLTHIAZOLE (I) 40 gms. of 2-acetamino-5-morpholinomethyl thiazole M.P. 125-127 C. are dissolved in 200 cc. of water and 100 cc. conc. HCl and stirred on the steam bath two hours. The solution is cooled, made basic with sodium carbonate and extracted with chloroform. The chloroform is evaporated off and the residue recrystallized from benzene. The crystals so obtained melt at 148-52 C.

2-AMINO-4-MORPHOLINOMETHYLTHIAZOLE (II) To a solution of 26.2 g. 2-amino-4-chloromethylthiazole 3,169,954 Patented Feb, 16, 1965 hydrochloride 7.5 g. Na CO 10 cc. H 0, and 150 cc. of ethanol there is added 25 g. of morpholine. The reaction mixture is stirred and heated on the steam bath for 2 hours.

After addition of cc. of water the alcohol is distilled off and the resulting solution extracted 3 times with 100 cc. of chloroform. After drying the extract over anhydrous Na SO the chloroform was distilled off leaving 16 g. of light tan product.

2-AMINO-4-PHENYL-5-DIMETHYL- I AMINOMETHYLTHIAZOLE (III) Twenty-four and five tenths grams of 2-acetamino-4- phenyl-5-dimethylaminomethylthiazole M.P. 157-160" C., 85 cc. of water and 42.5 cc. conc. HCl are stirred on the steam bath 2.5 hours. After cooling 30% NaOH is added below 40 C. until strongly basic. The product is filtered off, washed with water and air-dried, obtaining a material melting at 146-7 C.

2-AMINO-S-PIPERIDINOMETHYLTHIAZOLE (IV) 2-AMIN 0-5 -DI( fi-CYANOETHYL) AMINOMETHYLTHIAZOLE (V) The process of preparing Compound IV is carried out except using 123 g. of diQQ-cyanoethyl) amine in place of piperidine the product obtained being a sticky solid.

2-AMINO-4-PHENYL-S-PIPERIDINO- METHYLTHIAZOLE (VI) The procedure for Compound IV is carried out except using 219 g. of Z-acetamido-4-phenylthiazole (M.P. 209- 212 C.). The resulting amine melts at 22630 C.

2-AMINO-4-METHYL-5-PIPER- IDINOMETHYLTHIAZOLE (VII) The procedure for Compound IV is carried out except using 159 g. of 2-acetamido-4-methylthiazole (M.P. 125- 9 C.). The resulting amine melts at -l44 C.

2-AMINO-4-DIMETHYLAMINO- METHYLTHIAZOLE (VIII) J. A. C. S., 68, 2155 (1946).

Compounds I, II, IV and VII illustrate the preferred 2-aminothiazoles having the above general formula wherein R is hydrogen. Additional compounds of this group prepared similarly and described in more detail below are:

2-arnino-4-piperidinomethylthiazole Z-amino-5-methyl-4-piperidinomethylthiazole The preparation of representative dyes contemplated by the invention is illustrated by the following examples.

Example 1 To a solution of 1.8 g. NaNO in 13 cc. cone. H SO 25 cc. of 1:5 acid (propionic-acetic) was added below 25 C. At 0-5 C. a solution 0154.18 g. (0.021 m.) Z-amino- 5-n1orpholiiiomethylthiaiole (I'above) in 25 131:5 acid,

After two hours of stirring at 05 C. the diazo solution fibers in fast violet shades.

The dye has the following structure.

omen, HC'.V--N v H o ivcrn- (i-IEN-O-morn):

cmcfii s Y i I i Example 2 To a slurry of 1.2.g. (0.005 m.) 2-acetamido 5-piperidylrnethylthiazole in 12 cc. of water was added 7 cc; of

' cone. H 80 at such rate that the temperature rose above 80 C. but not above 95- C. The solution was allowed to cool for 30 minutes, thenchilled' to 0 C. A solution of O.36 g.'NaNO in2.5. c'c. H 50 was added below 5 C. After two hours of stirring at 0+5? C. the 'diazo solution was added to' 0.94 g. (0.005 m.) 'of N-ethybNfi-cyama a I ethyl-m-toluidinein 50 cc. of 6% H01 and-ice." After two hours'o'f stirring without further cooling the mix was neutralized with aqueouscarbon-ate'. The dye was isolated as above, obtaining a product which imparted fast violet shades to anacrylic polymer cloth.

E xar fiple 3 V I In the manner of Example 2.1.78 g. of 2-aceta1nido-4- methyl-5-morpholinomethylthiazole was. hydrolyzed and 10 diazotized and coupled with 0.9 g. of diphenylarnine. The

dye imparts fast blue shades to acrylic polymers. The dye has the following-formula current 0113c 'CH2--C 2 I Example4 'In the manner of Example 1, 3.3 g. of 2-arnino-4-dimethylarninomethylthiazole (VIII above) was di-azotized 20 and coupled with N,N-dimethylaniline.' The dye imparts fast violet shades to acrylic polymers; The'dyes described in the following table are prepared in the manner of the above exarnples i 7 Color of Dye R1 R: I Coupler on acrylic I, er

-/CH2-CVHV2 0 NCH'.= H N-etbyl-N-fl-cyauo- Violet.

\ r ethyl-m-toluidine...

CHa-CH: o11'=-cH1 0 NoH2.- H:- Diphenylamine Do."

(Mi -CH1 CHr-CH:

' o Noni-Q cent-m; N-ethyl-N-fl-hydroxy- Do.

\ ethylaniline.

CH2-C11I OHZ-CH1 C a NGH2+- H. Di-B-eyan0ethyl-= Red.

aniline. GET-CH2 CH -CH;

CH, NCHr- CHa- Di-fl-hydroxyethyl- Blue-violet.

aniline.

GE -OH; I

(CNCH CHz)gNGHi; H- N-B-hydroxyethyh Do.

7 diphenylamine. H- cHmNom- N,N-diethyl-m Redviolet..

, chloroaniline.

0nr-oH, H O\V '/NCH2-; Ng-cyanoiathyl- Do.

lphen amine.

CHQCH? y GHQ-DEB I OH; NOH1- CuHy- N-cyanoethylaniline D0.

H2- H2 r (GHs)2NCH2- 05115-2; do Do.

/CH1-CH1 I -0 Norn- H- N,N-dimethylanilinei. Do.

CHr-CH:

I /CHr-CH: GHQ- c NCHzd0 -Q. D0.

' CHf-CH; om-0H, CH3- 0 Noni- .-do Do.

CH --CH in which R and R represent a member of the class consisting of lower alkyl, lower hydroxyalkyl, lower cyanoalkyl, hydrogen and phenyl, and R represents a member of the class consisting of methyl, chlorine and hydrogen,

R '=a member of the class consisting of piperidinomethyl, lower dialkylaminomethyl, di(fl-cyanoethyl) aminomethyl and morpholinomethyl radicals, and

R '=a member of the class consisting of hydrogen,

phenyl, lower alkyl, piperidinomethyl and morpholinomethyl, R being difierent from R 2. Monoazo dyestuffs having the general formula wherein R'=a residue of an N,N-lower dialkyl aniline coupling component and R =a piperidinomethyl radical.

3. Monoazo dyestuffs having the general formula wherein R=a residue of an N,N-1ower dialkyl aniline coupling component and R =a morpholinornethyl radical. 4. The monoazo dye having the formula CH,0H2 HC-N 0 Nom J 'N=NC N( s)2 \CH4CZ s 5. The monoazo dye having the formula CH HCN CHQCHRCN 0 "H -C H2 1 0 H9 NCHZ CH C H 5 6. The monoazo dye having the formula OHg-CHg CH3CN czHs CHZCH2 7. The monoazo dye having the formula GHQ-CH2 HC-N 0 m 0 NCHz N=N--N CHzCHz \S/ H3 \CH2CH2CN 8. The monoazo dye having the formula CHz-CH C -N 0 NOI-hll llN=N O CHg--Cq S References Cited in the file of this patent UNITED STATES PATENTS 2,726,237 Towne et al. Dec. 6, 1955 2,730,523 Dickey et a1 Jan. '10, 1956 2,852,504 Towne et a1 Sept. 16, 1958 OTHER REFERENCES Sprague et al.: J. A. C. 8., vol. 68, pp. 21554159 (1946).

Albertson: J. A. C. S.,vol. 70, pp. 669-670 (1948). 

1. MONOAZO DYESTUFFS HAVING THE GENERAL FORMULA 